US5122589A - Imido/siloxane bismaleimide/aromatic diamine prepolymers - Google Patents

Imido/siloxane bismaleimide/aromatic diamine prepolymers Download PDF

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US5122589A
US5122589A US07/506,743 US50674390A US5122589A US 5122589 A US5122589 A US 5122589A US 50674390 A US50674390 A US 50674390A US 5122589 A US5122589 A US 5122589A
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bismaleimide
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prepolymer
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Yves Camberlin
Philippe Michaud
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Huntsman Advanced Materials Americas LLC
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Rhone Poulenc Chimie SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/404—Imides, e.g. cyclic imides substituted imides comprising oxygen other than the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/125—Unsaturated polyimide precursors the unsaturated precursors containing atoms other than carbon, hydrogen, oxygen or nitrogen in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/455—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyamide, polyesteramide or polyimide sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention features heat-curable imido prepolymers having a very low viscosity in the molten state, measured under those conditions more fully described below, ranging from 0.1 Pa.s to 50 Pa.s, and which comprise the copolymerizates, in a homogeneous liquid medium at a temperature ranging from 50° C. to 180° C., of:
  • N,N'-bismaleimide having the formula: ##STR1## in which each of the symbols Z, which may be identical or different, is H, CH 3 or Cl; and the symbol A is a divalent radical selected from among the following: cyclohexylenes, phenylenes, 4-methyl-1,3-phenylene, 2-methyl-1,3-phenylene, 5-methyl-1,3-phenylene and 2,5-diethyl-3-methyl-1,4-phenylene, and the radicals of the formula: ##STR2## wherein B is a single valence bond or one of the groups: ##STR3##
  • said at least one N,N'-bismaleimide (b) comprising a diorganopolysiloxane moiety has the following general formula: ##STR4## in which X, which is in an ortho, meta or para position in relation to the carbon atom of the benzene ring which is bonded to nitrogen, is a single valence bond or one of the following atoms or groups: ##STR5## each of R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 , which may be identical or different, is a monovalent hydrocarbon radical selected from among linear or branched chain alkyl radicals having from 1 to 12 carbon atoms, or substituted such alkyl radicals bearing one or more chlorine, bromine or fluorine substituents or by a --CN group; a phenyl radical optionally substituted by one or more alkyl and/or alkoxy radicals having from 1 to 4 carbon atoms or by one or more chlorine
  • said at least one aromatic diprimary diamine (c) comprises:
  • each of the symbols R 9 , R 10 , R 11 and R 12 which may be identical or different, is a methyl, ethyl, propyl or isopropyl radical; each of the symbols T, which may be identical or different, is a hydrogen atom or a chlorine atom; and the symbol E is a divalent radical selected from among: ##STR7##
  • (c3) a compound having the general formula: ##STR8## in which the amino radicals are in a meta or para position relative to each other; and each of the symbols R 13 , which may be identical or different, is a methyl, ethyl, propyl or isopropyl radical;
  • copolymerizates further include an additive (f) which comprises either an acrylate reactant (f1) or an unhalogenated epoxy resin (f2):
  • said acrylate reactant (f1) comprising at least one compound of the general formula:
  • R 14 is a hydrogen atom or a methyl radical
  • n is a whole or fractional number equal to at least 1 and not greater than 8
  • the symbol G is an organic radical or valency n which comprises a linear or branched chain, saturated aliphatic radical having from 1 to 30 carbon atoms and which may contain one or more oxygen bridges and/or one or more free hydroxyl functional groups; or an aryl or arylaliphatic radical having from 6 to 150 carbon atoms and including a benzene nucleus which may be substituted by one to three alkyl radicals having from 1 to 5 carbon atoms, or a plurality of benzene nuclei optionally substituted as indicated above, bonded together by a single valence bond, an inert group or an alkylene radical having from 1 to 3 carbon atoms, with the proviso that said aromatic radical may also contain one or more bridging oxygen atoms and/or one or more free hydroxyl functional groups, and wherein the free
  • said unhalogenated epoxy resin (f2) comprising an epoxy resin having an epoxy equivalent weight ranging from 100 to 500 and which comprises a glycidyl ether prepared by reacting epichlorohydrin with a divalent polyphenol selected from among bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methylphenylmethane or bis(4-hydroxyphenyl)-tolylmethanes; resorcinol, hydroquinone, pyrocatechol, 4,4'-dihydroxydiphenyl, and the products of condensation of the above-mentioned phenols with an aldehyde.
  • a divalent polyphenol selected from among bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methylphenyl
  • N,N'-4,4'-diphenylmethanebismaleimide is preferred, either alone or mixed with N,N'-2-methyl-1,3-phenylenebismaleimide, N,N'-4-methyl-1,3-phenylenebismaleimide and/or N,N'-5-methyl-1,3-phenylenebismaleimide.
  • siloxane bismaleimides (b) of formula (II) when y and/or z are greater than 1, a polymeric structure exists that can be a single compound, but in most cases is a mixture of different compounds having the same chemical structure, which differ in the number of recurring units in their molecule; this imparts an average value of y and/or z which may be whole or fractional.
  • any one of the compounds of formula (II) can be employed.
  • X --O--;
  • x 2, 3 or 4;
  • y+z ranges from 0 to 100 and preferably from 4 to 70.
  • siloxane bismaleimides (b) which are suitable, especially representative are those of the formulae: ##STR9##
  • siloxane bismaleimides of formula (II) are compounds which are prepared by reacting maleic anhydride, in the presence of a dehydrating agent, of a tertiary amine, of an organic diluent and of a catalyst, with a diamine comprising a diorganopolysiloxane moiety and having the formula: ##STR10## in which X, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , x, y and z are as defined above for the formula (II). Further description of such siloxane bismaleimides and a process for the preparation thereof are particularly set forth in French Patent Application FR-A-2,611,728.
  • 4,4'-Diaminodiphenylmethane is preferably employed according to the present invention.
  • hindered diamines can be prepared according to the processes described in British Patent GB-A-852,651 and U.S. Pat. No. 3,481,900. According to the present invention, 4,4'-diamino-3,3',5,5'-tetramethyldiphenylmethane, 4,4'-diamino-3,3',5,5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane and mixtures thereof are the preferred.
  • acrylate reactant (fl) the following are particularly representative:
  • G is a monovalent organic radical of the formula:
  • G 1 is a linear or branched chain alkyl radical having from 1 to 6 carbon atoms or a phenyl radical, and m is an integer equal to zero, 1, 2, 3, 4 or 5;
  • G is a divalent organic radical of the formula:
  • G 2 is a linear or branched chain alkylene divalent radical having from 2 to 9 carbon atoms and optionally comprising one or more oxygen bridges or a radical of the formula: ##STR11## in which the symbol U is a single valence bond or one of the groups: ##STR12## wherein each of the symbols p and q, which may be identical or different, is an integer equal to zero, 1, 2, 3, 4 or 5;
  • n 3 or 4
  • G is a trivalent or tetravalent organic radical derived from a linear or branched chain saturated aliphatic residue having from 3 to 20 carbon atoms and optionally comprising one or more oxygen bridges and/or one or more free hydroxyl functional groups;
  • the novolak epoxy(meth)acrylates (f1.4) are known materials, certain of which are available commercially. They can be prepared by reacting (meth)acrylic acids with an epoxy resin of the novolak type, the latter being the product of reaction of epichlorohydrin and of phenol/formaldehyde polycondensates [in the formula (IX) given above, R 15 is then a hydrogen atom] or of cresol/formaldehyde polycondensates [in said formula, R 15 is then a methyl radical].
  • an epoxy resin of the novolak type the latter being the product of reaction of epichlorohydrin and of phenol/formaldehyde polycondensates [in the formula (IX) given above, R 15 is then a hydrogen atom] or of cresol/formaldehyde polycondensates [in said formula, R 15 is then a methyl radical].
  • acrylate reactant (f1.4) particularly representative are the novolak epoxy acrylates of formula (IX) in which R 14 and R 15 are each a hydrogen atom and t is a whole or fractional number ranging from 0.1 to 5.
  • exemplary of the acrylate reactant (f1.5), particularly representative are mixtures of novolak epoxy(meth)acrylates (f1.4) with not more than 30% by weight, based on the weight of the mixture (f1.4)+(f1.3), of a triacrylate and/or of a trimethacrylate corresponding to the definitions given above in connection with the acrylate reactant (f1.3) and, in particular, the mixtures of the suitable novolak epoxy acrylates referred to immediately above with not more than 25% by weight, relative to the weight of the mixture, of a suitable triacrylate and/or of a trimethacrylate selected from those mentioned immediately above.
  • the acrylate reactant (fl) which is preferably used is selected from among di(monooxyethylated)bisphenol A di(meth)acrylates, di(dioxyethylated)bisphenol A di(meth)acrylates, the novolak epoxy acrylates of formula (IX) in which R 14 and R 15 are each a hydrogen atom and t is a whole or fractional number ranging from 0.1 to 5, these compounds being used alone or mixed with not more than 25% by weight, relative to the weight of the mixture, of trimethylolpropane triacrylate.
  • epoxy equivalent weight the weight of resin (in grams) containing one epoxy functional group.
  • An epoxy resin which has an epoxy equivalent weight ranging from 150 to 300 is preferred. As regards the physical characteristics of this resin, these range from those of liquid resins of low viscosity (approximately 2 ⁇ 10 -3 Pa.s at 25° C.) to those of pasty resins having a melting point on the order of 60° C.
  • the preferred resins are the glycidyl ethers of bis(hydroxyphenyl)alkanes referred to above in connection with the detailed description of the resin (f2).
  • (d2) a compound comprising a mixture of (i) a monomer of the formula: ##STR16## in which the allyloxy or methallyloxy radical is in an ortho, meta or para position in relation to the carbon atom of the benzene ring which is bonded to nitrogen, with: (ii) at least one monosubstituted derivative of the formula: ##STR17##
  • the proportions of the various constituents of the mixture of the compounds of formulae (X), (XI) and optionally (XII) may vary over wide limits.
  • the proportions of the constituents are selected within the following limits (expressing the weight percentage of each of the constituents in the mixture):
  • this advantageously comprises:
  • the maleimides of formula (X) are known compounds which are described in European Patent Application EP-Al-0,208,634.
  • the crude product produced by the process described in European Patent Application EP-A-0,274,967 is preferably employed as the compound comprising a mixture of N-(meth)allyloxyphenylmaleimide of formula (X) with one or more (meth)allylated substitution derivatives of formula(e) (XI) and optionally (XII).
  • this is advantageously selected from among: vinyl pyridines, N-vinylpyrrolidone, allyl isocyanurate, triallyl isocyanurate, vinyltetrahydrofuran and mixtures thereof.
  • a catalyst which may be either (el) a radical polymerization initiator such as, for example, dicumyl peroxide, lauroyl peroxide or azobisisobutyronitrile, or (e2) an imidazole compound.
  • the said imidazole compound (e2) advantageously has the general formula: ##STR19## in which each of R 16 , R 17 , R 18 and R 19 , which may be identical or different, is a hydrogen atom, an alkyl or alkoxy radical having from 1 to 20 carbon atoms, or a vinyl, phenyl or nitro radical, with the proviso that R 18 and R 19 may together form, with the carbon atoms from which they depend, a single ring member such as, for example, a benzene ring, and with the further proviso that R 16 may comprise a carbonyl group bonded to a second imidazole ring.
  • optional imidazole compounds (e2) particularly representative are imidazole or glyoxaline, 1-methylimidazole, 2-vinylimidazole, 1,2-dimethylimidazole, 1-vinylimidazole, 1-vinyl-2-methylimidazole, benzimidazole and carbonyldiimidazole.
  • the preferred prepolymers in accordance with the present invention are those which comprise the polymerizate of:
  • the preferred polymers are not only those described immediately above, but also those comprising the various preferred embodiments described earlier.
  • the amounts of reactants (a) and (c) are selected such as to generally provide, by weight relative to the total weight of these constituents:
  • siloxane bismaleimide (b) of formula (II) this generally represents less than 40%, and preferably from 5% to 30%, of the total weight of the reactants (a)+(c).
  • this generally represents less than 60%, and preferably from 5% to 50%, of the total weight of the reactants (a)+(c).
  • the optional catalyst (e) depending on its nature ad depending on the desired rate of polymerization at the processing stage, it is generally employed in a proportion ranging from 0.01% to 1% by weight relative to the total weight of the reactants (a)+(b)+(c)+optionally (d) and, preferably, ranging from 0.05% to 0.5%.
  • the required additive (f) comprising an acrylate reactant (fl) or an epoxy resin (f2)
  • this is advantageously employed in an amount which generally represents from 1% to 60%, and preferably from 5% to 30%, of the weight of the total weight of the constituents (a)+(b)+(c)+(f)+optionally (d).
  • adjuvants may be incorporated in the prepolymers according to the invention.
  • These adjuvants may be, for example, stabilizers or degradation inhibitors, lubricants or demolding agents, colorants or pigments, pulverulent or particulate fillers such as silicates, carbonates, kaolin, chalk, powdered quartz, mica or ballotini.
  • adjuvants which modify the physical structure of the product obtained such as, for example, blowing agents or fibrous reinforcing agents, such as, especially, carbon, polyimide or aromatic polyamide fibrils, or whiskers.
  • the process for the preparation of the prepolymers of the invention is such that they are ready for use and exhibit sufficient flexibility and adhesiveness as a thin layer.
  • an intimate mixture of the bismaleimide(s) (a) and of the amine reactant (c) is produced first.
  • the mixture (a)+(c) is melted, in the absence of the optional catalyst (e).
  • This operation is carried out under stirring and at a temperature not exceeding the melt temperature of that maleimide which is the most difficult to liquefy, generally ranging from 50° to 180° C., and preferably from 80° C. to 170° C., until a homogeneous liquid mixture is obtained (stage 1).
  • the following constituents are then added in succession to the molten mixture, which is stirred and maintained at a temperature identical with or different from that used in the preceding stage, generally ranging from 50° C. to 180° C., and preferably from 80° C. to 170° C.: in a first step, the siloxane bismaleimide (b), then, in a second step, the additive (f), with care being taken to maintain a homogeneous liquid mixture; and, once this additive has been introduced, the prepolymer formed is immediately withdrawn from the reactor used for the preparation thereof (stage 2).
  • the optional reactant (d) and/or the optional catalyst (e) are used, these are generally introduced at the beginning of stage 2 (into the molten mixture which, as indicated above, is stirred and maintained at a temperature identical with or different from that used in stage 1, ranging from 50 C to 180° C., and preferably from 80° C. to 170° C.) before the introduction of the other constituents (b) and (f) of the reaction mixture. Precautions will be taken in this case to permit the reaction mixture to react under stirring for a period of time ranging, for example, from 1 minute to 15 minutes, before introducing the other constituents (b) and (f).
  • the melt viscosity of the prepolymers thus obtained can be easily adjusted to the desired value, which ranges from 0.1 Pa.s to 50 Pa.s, especially by modifying the nature and the respective proportions of the reactants used and the temperature and the duration of the various stages of the process of manufacture described above.
  • the above process can be carried out not only in a melt, but also in the presence of variable amounts of a polar liquid such as, for example: cresol, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methyl ethyl ketone, dioxane or cyclohexanone.
  • a polar liquid such as, for example: cresol, dimethylformamide, N-methylpyrrolidone, dimethylacetamide, methyl ethyl ketone, dioxane or cyclohexanone.
  • the prepolymers according to the invention can be directly used, for example for impregnating conductors or for producing moldings merely by hot casting. It is also possible, after cooling and grinding, to employ these prepolymers in the form of powders, for example to produce compression-molded shaped articles, optionally in combination with fibrous or pulverulent fillers.
  • the prepolymers can also be employed in solution for the preparation of coatings, of adhesive bondings, of laminated materials comprising woven or nonwoven sheets, of one-directional elements or of natural or synthetic chopped fibers, such as, for example, filaments or fibers made of glass, boron, carbon, tungsten, silicon, polyamideimide or aromatic polyamide.
  • the prepolymers according to the present invention are of very particular interest for the production of solvent-free preimpregnated intermediate articles.
  • the impregnation of the fibrous material can be carried out by the usual techniques such as immersion, knife or curtain coating, or impregnation by transfer.
  • the transferable film and the preimpregnated articles can be employed directly or can be stored for subsequent use; their properties are preserved remarkably well over the course of cold storage at a temperature of from 0 to 10° C.
  • the prepolymers employed for this application preferably have a melt viscosity ranging from 2 Pa.s to 50 Pa.s.
  • the preimpregnated materials can be used for the production of components of various shapes and functions in many industries such as, for example, in aeronautics. These components, which may be articles of revolution, are produced by stacking a plurality of layers of prepregs onto a former or a support.
  • the crosslinking is then carried out under the usual technological conditions relating to composite materials, and in particular at temperatures ranging from 100° to 300° C.
  • the prepregs can also be employed as reinforcements, or means for repairing deteriorated or damaged articles.
  • the prepolymers used in this particular technique preferably have a melt viscosity ranging from 0.1 Pa.s to 2 Pa.s.
  • the melt viscosity as referred to herein was the dynamic viscosity of the prepolymer obtained at the time of casting, upon completion of the process carried out in bulk; it was measured at 80° C. ⁇ 0.1° C. using a Contraves Rheomat 30 viscometer equipped with a rotor rotating at a rate of 13 s -1 ; its value is reported in Pa.s.
  • the softening point is the approximate temperature at which a glass rod 6 mm in diameter can easily be penetrated a few mm into the prepolymer.
  • the glass transition temperature (Tg) corresponds to the abrupt drop in the modulus of elasticity as a function of temperature. It was determined on a graph plotting the variation in the modulus of elasticity as a function of temperature, variations which were measured using dynamic mechanical analysis, with the aid of a Dupont DMA model 982 apparatus, at a rate of temperature increase of 3° C./min.
  • the test specimens were conditioned at RHO (zero relative humidity), i.e., they were placed in a desiccator over silica gel and dried for 24 hours at ambient temperature at 0.66-1.33 ⁇ 10 2 Pa before the measurements were carried out.
  • dumbbell-type test specimens conditioned at RHO, according to ASTM Standard D 638M.
  • Stage 1 The reactor was immersed in an oil bath preheated to 160° C. and the mixture was stirred until the ingredients introduced had completely melted and a homogeneous liquid mass had been obtained. This stage was carried out for 5 minutes.
  • Stage 2 The molten mixture obtained was cooled to 120° C. and 8 g of N-vinyl-2-pyrrolidone were introduced, and the entire mass was then permitted to react for 8 minutes, under stirring.
  • the prepolymer thus obtained was flexible and tacky at ambient temperature (20° C.). It had a softening point of approximately 5° C. Its viscosity at 80° C. was 3 Pa.s.
  • the plaques based on the cured polymer were cut to produce test specimens of appropriate dimensions, which were used to measure the following: the glass transition temperature (Tg), the flexural modulus (Mf), the flexural rupture strength (Sr), the unnotched Charpy impact strength (Si) and the tensile elongation at break (Eb).
  • Tg glass transition temperature
  • Mf flexural modulus
  • Sr flexural rupture strength
  • Si unnotched Charpy impact strength
  • Eb tensile elongation at break
  • the prepolymer obtained in these conditions had a softening point of 50° C. and a viscosity at 80° C. which was on the order of 100 Pa.s. This made it difficult to employ such prepolymer for producing solvent-free preimpregnated intermediate articles (the prepolymer was too viscous and the impregnation of the fibers resulted in a considerable distortion of the sheet, which militates against such an application).
  • This bismaleimide had the following formula: ##STR20##
  • the reactor was then placed into an oil bath preheated to 55° C. and the catalyst was then added.
  • the latter was the Karsted catalyst (complex based on elemental platinum and on 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ligands): it was in solution in toluene (concentration of 3.5% by weight) and 1.49 cm 3 of this catalyst solution were introduced with a syringe; the ratio (weight of elemental platinum introduced/weight of the reaction mass) was equal to 91 ⁇ 10 -6 .
  • the molecular weight was on the order of 1,100. Under these conditions, the degree of conversion of the reactants introduced was 100% (neither amine nor hydrogenated siloxane oligomer was detected by NMR and infrared analysis) and the weight yield of the desired diamine was 100%.
  • each funnel was rinsed with 5 cm 3 of acetone, which were then added to the reaction mass, which was maintained stirred for an additional 15 minutes.
  • the reaction mixture was maintained under reflux with stirring for 2 hours, 30 minutes. The temperature was then decreased to 20° C.
  • the reaction mixture was diluted with 80 cm 3 of iced water (5° C.) with vigorous stirring, and the oily product present was then extracted with 80 cm 3 of ethyl acetate.
  • the organic phase obtained was washed with three 80-cm 3 portions of water to attain pH 6 in the aqueous washings, and was then dried for 2 hours over anhydrous sodium sulfate.
  • the ethyl acetate was removed from the organic phase by evaporation, this operation being completed under reduced pressure (approximately 70 Pa) at 60° C., and 30.3 g (i.e., a weight yield of 96% relative to the theoretical) of a viscous, orangy-brown product were collected, whose NMR spectrum was in agreement with the structure of the desired bismaleimide given at the beginning of this example.
  • the molecular weight was on the order of 1,260.
  • Stage 1 The reactor was immersed in an oil bath preheated to 160° C., and the mixture was stirred until the ingredients introduced had melted completely and a homogeneous liquid mass has been obtained. This stage was carried out for 5 minutes.
  • Stage 2 The molten mixture obtained was cooled to 120° C. and 8 g of N-vinyl-2-pyrrolidone were introduced, and the entire mass was then permitted to react for 8 minutes under stirring.
  • an epoxy resin 15 g of an epoxy resin were then added to the reaction mass, continuously under stirring and maintained at 120° C., the resin being a glycidyl ether prepared by reacting epichlorohydrin with 2,2-bis(4-hydroxyphenyl)propane (or bisphenol A) and having an epoxy equivalent weight of 188; its viscosity at 25° C. was 10.5 Pa.s; it is available commercially under the registered trademark Araldite of the Ciba company, type LY 556.
  • the liquid reaction mass obtained was immediately cast into a mold preheated to 150° C.
  • the prepolymer thus obtained was flexible and tacky at ambient temperature (20° C.). It had a softening point of approximately 10° C. Its viscosity at 80° C. was 4 Pa.s.
  • the plaques based on cured polymer were cut to produce test specimens of appropriate dimensions, which were used for measuring: the glass transition temperature (Tg), the flexural modulus (Mf), the flexural rupture strength (Sr), the unnotched Charpy impact strength (Si) and the tensile elongation at break (Eb).
  • Tg glass transition temperature
  • Mf flexural modulus
  • Sr flexural rupture strength
  • Si unnotched Charpy impact strength
  • Eb tensile elongation at break
  • the prepolymer obtained under these conditions had a softening point of 50° C. and a viscosity at 80° C. which was on the order of 100 Pa.s. This made it difficult to produce solvent-free preimpregnated intermediate articles therefrom (the prepolymer was too viscous and the impregnation of the fibers resulted in a considerable distortion of the sheet, which militates against such application).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silicon Polymers (AREA)
  • Epoxy Resins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US07/506,743 1989-04-10 1990-04-10 Imido/siloxane bismaleimide/aromatic diamine prepolymers Expired - Lifetime US5122589A (en)

Applications Claiming Priority (2)

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FR8904936 1989-04-10
FR8904936A FR2645540B1 (fr) 1989-04-10 1989-04-10 Polymeres a groupements imide a base de maleimides dont un bismaleimide siloxane et de diamines aromatiques et leur procede de preparation

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US (1) US5122589A (de)
EP (1) EP0397581B1 (de)
JP (1) JP2597916B2 (de)
KR (1) KR900016318A (de)
AT (1) ATE102233T1 (de)
AU (1) AU631862B2 (de)
BR (1) BR9001678A (de)
CA (1) CA2013962C (de)
DE (1) DE69006908T2 (de)
FR (1) FR2645540B1 (de)
IL (1) IL93615A0 (de)
PT (1) PT93710A (de)
ZA (1) ZA902700B (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439986A (en) * 1992-08-03 1995-08-08 Showa Highpolymer Co., Ltd. Thermo-curable resin composition, and a method for producing a copper-clad laminate using same
WO2009145779A1 (en) * 2008-05-30 2009-12-03 Henkel Corporation Oligomeric adducts of bismaleimide, diamine, and dithiol
CN109054381A (zh) * 2018-07-06 2018-12-21 苏州生益科技有限公司 改性马来酰亚胺树脂组合物及其制备的半固化片和层压板
WO2023115686A1 (zh) * 2021-12-22 2023-06-29 苏州大学 无卤无磷阻燃形状记忆双马来酰亚胺树脂及其制备方法

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2645539B1 (fr) * 1989-04-10 1991-06-14 Rhone Poulenc Chimie Polymeres a groupements imides faits a partir de diamines encombrees
FR2653130B1 (fr) * 1989-10-16 1992-01-03 Rhone Poulenc Chimie Polymeres a groupements imides faits a partir de diamines encombrees.
JP2012236920A (ja) * 2011-05-12 2012-12-06 Hitachi Chemical Co Ltd 熱硬化性樹脂組成物、これを用いたプリプレグ、積層板及びプリント配線板
JP6322919B2 (ja) * 2012-07-25 2018-05-16 日立化成株式会社 熱硬化性樹脂組成物、これを用いたプリプレグ、積層板及びプリント配線板
CN116120560B (zh) * 2022-10-11 2024-04-12 苏州生益科技有限公司 改性双马来酰亚胺预聚物的制备方法、树脂组合物及树脂组合物的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206383A1 (de) * 1985-06-08 1986-12-30 Dsm Resins B.V. Bismaleidzusammensetzungen
EP0284524A1 (de) * 1987-03-10 1988-09-28 Rhone-Poulenc Chimie Hitzestabile Polymere auf der Basis von Maleimiden, wovon eins ein Bismaleimid-Siloxan ist, und aromatischen Diaminen, Verfahren zu ihrer Herstellung
US4883858A (en) * 1987-08-25 1989-11-28 Nippon Oil And Fats Co., Ltd. Thermosetting resin from amine terminated amic acid and bis-maleimide
US4959443A (en) * 1988-05-17 1990-09-25 Mitsui Toatsu Chemicals, Inc. Thermosetting resin composition from bis maleimide and aromatic amine resin

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2609467B1 (fr) * 1987-01-09 1989-06-09 Rhone Poulenc Chimie Compositions thermodurcissables a base de groupements imide et epoxy
FR2638163B1 (fr) * 1988-10-26 1991-01-11 Rhone Poulenc Chimie Polymeres a groupements imides faits a partir de diamines encombrees
FR2645539B1 (fr) * 1989-04-10 1991-06-14 Rhone Poulenc Chimie Polymeres a groupements imides faits a partir de diamines encombrees
FR2653130B1 (fr) * 1989-10-16 1992-01-03 Rhone Poulenc Chimie Polymeres a groupements imides faits a partir de diamines encombrees.

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0206383A1 (de) * 1985-06-08 1986-12-30 Dsm Resins B.V. Bismaleidzusammensetzungen
EP0284524A1 (de) * 1987-03-10 1988-09-28 Rhone-Poulenc Chimie Hitzestabile Polymere auf der Basis von Maleimiden, wovon eins ein Bismaleimid-Siloxan ist, und aromatischen Diaminen, Verfahren zu ihrer Herstellung
US4883858A (en) * 1987-08-25 1989-11-28 Nippon Oil And Fats Co., Ltd. Thermosetting resin from amine terminated amic acid and bis-maleimide
US4959443A (en) * 1988-05-17 1990-09-25 Mitsui Toatsu Chemicals, Inc. Thermosetting resin composition from bis maleimide and aromatic amine resin

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5439986A (en) * 1992-08-03 1995-08-08 Showa Highpolymer Co., Ltd. Thermo-curable resin composition, and a method for producing a copper-clad laminate using same
WO2009145779A1 (en) * 2008-05-30 2009-12-03 Henkel Corporation Oligomeric adducts of bismaleimide, diamine, and dithiol
CN109054381A (zh) * 2018-07-06 2018-12-21 苏州生益科技有限公司 改性马来酰亚胺树脂组合物及其制备的半固化片和层压板
CN109054381B (zh) * 2018-07-06 2020-09-11 苏州生益科技有限公司 改性马来酰亚胺树脂组合物及其制备的半固化片和层压板
WO2023115686A1 (zh) * 2021-12-22 2023-06-29 苏州大学 无卤无磷阻燃形状记忆双马来酰亚胺树脂及其制备方法

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CA2013962A1 (fr) 1990-10-10
FR2645540A1 (fr) 1990-10-12
BR9001678A (pt) 1991-05-14
KR900016318A (ko) 1990-11-13
JP2597916B2 (ja) 1997-04-09
EP0397581A1 (de) 1990-11-14
PT93710A (pt) 1990-11-20
DE69006908D1 (de) 1994-04-07
AU631862B2 (en) 1992-12-10
ATE102233T1 (de) 1994-03-15
IL93615A0 (en) 1990-12-23
AU5302190A (en) 1990-10-11
ZA902700B (en) 1991-01-30
DE69006908T2 (de) 1994-07-14
JPH0314837A (ja) 1991-01-23
CA2013962C (fr) 1994-05-24
EP0397581B1 (de) 1994-03-02

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